JP3057246B2 - Solid color developing agent for silver halide color photographic light-sensitive material and method of processing silver halide color photographic light-sensitive material processed using the processing agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a processing agent for a silver halide photographic light-sensitive material, and more particularly, to a processing agent for a silver halide color photographic light-sensitive material (hereinafter sometimes referred to as "light-sensitive material"). The present invention relates to a solid color developing processing agent and a processing method of a silver halide color photographic light-sensitive material using the processing agent.

[0002]

BACKGROUND OF THE INVENTION Processing of a light-sensitive material basically comprises two steps of color development and desilvering, and desilvering comprises a bleaching and fixing step or a bleach-fixing step. In addition, rinsing processing, stabilizing processing, and the like are added as additional processing steps.

In color development, exposed silver halide is reduced to silver and simultaneously oxidized aromatic primary
Secondary amine developing agents react with the coupler to form a dye. In this process, the halogen ions generated by the reduction of silver halide are eluted and accumulated in the developer, while the color developing agent is consumed or is accumulated and taken out in the photosensitive material, and the concentration of those components decreases. To go. Therefore, in a developing method in which a large amount of photosensitive material is continuously processed by an automatic developing machine or the like, a means for keeping the components of the color developing solution within a constant concentration range in order to avoid a change in the development finish characteristics due to a change in the component concentration. is necessary. As such means, a method of replenishing a replenisher for compensating for the deficient components and diluting unnecessary increase components is usually employed. Since the replenishment of the replenisher inevitably causes a large amount of overflow and is discarded, this method is a serious problem in terms of economy and pollution. Therefore, in recent years, in order to reduce the overflow solution, a method of regenerating a developer by an ion exchange resin method or an electrodialysis method, a method of replenishing with a low concentration, and further, a method of adding a regenerating agent to the overflow solution and using it as a replenisher again Have been proposed and put to practical use.

[0004] Regeneration of the developer is carried out by removing bromide, which is an unnecessary accumulation component, to make up for the deficient component. In this method (ion exchange resin method and electrodialysis method), the developer component is determined by chemical analysis. If it is not constant, there is a disadvantage that the development processing characteristics of the photosensitive material are impaired,
Since it requires complicated management, it is almost impossible to introduce it in small-scale laboratories or mini-labs without special skills. There is also a disadvantage that the initial cost is extremely high.

Further, a method of adding a regenerating agent to the overflow solution to regenerate it as a replenisher requires no special skills, but requires a space such as a stock tank, and has a drawback that it is complicated for a developer. It is extremely difficult to introduce a method into a minilab. However, the concentrated low replenishment method is particularly suitable for a small lab such as a mini lab because the method does not require a new device and the process management is easy. However, this method also has some disadvantages.

That is, when preparing a concentrated replenisher, 4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) -m-toluidine (sesquisulfate monohydrate) was used as a color developing agent. In such a case, if the solubility of the color developing agent is low, for example, if the color developing agent is erroneously dissolved with a small amount of water (mis-dissolution of the replenisher), the color developing agent precipitates out and circulates in the color developing tank. There is a problem that a filter provided in the line may be clogged or a replenishment pump may be damaged.

[0007] Further, since the replenishment time of the replenisher in the replenishment tank is prolonged due to the low replenishment rate, the replenishment tank becomes extremely susceptible to the effect of air oxidation, which leads to deterioration in processing performance. With the recent expansion of the minilab market, the number of minilabs with a small processing amount tends to increase, and the deterioration of the liquid preservability in a replenishment tank has become more and more problematic.

[0008] Furthermore, in recent years, the problem of environmental pollution has been highlighted globally, and the disposal of plastic bottles for treating agents has become a serious problem. The current situation is that legislative and regulatory movements such as the mandatory use of garbage are becoming active.

[0009] In order to solve these problems, EP-456220 discloses powdering of a treating agent. However, it has the drawback of causing deterioration in solubility due to casing (agglomeration) due to storage over time, fatigue coloring due to moisture, oxygen, etc., and the possibility that fine powder will fly up during dissolution and be sucked in by workers. And there is a problem that the adverse effect on health may be feared, or the sowing of the processing agent component may be mixed into another photographic processing solution, thereby causing contamination and trouble. For this reason, a technique of granulating a photographic processing agent to form a granular mixture is disclosed in, for example, JP-A-2-09042, JP-A-2-09043,
2,843,484 and JP-A-3-39735, etc., but still have problems on occupational safety and health due to scattered chemical dust, contamination as impurities in other kinds of treatment liquids, or casing which settles and condenses on the bottom of the container when dissolved Phenomenon, coating the powder with its own wet film, causing problems such as inferior dissolution due to poor dissolution, etc., and the range of drugs suitable for powdering and granulation is extremely restricted. It is a fact.

[0010] Therefore, as a preferred form of the treatment agent taking advantage of these advantages of the dry state, tableting is disclosed in JP-A-51-61837.
No. has been proposed.

Although this method is very useful in terms of occupational safety and health because there is no scattering of chemicals, it can be said to be the best method since it has a multipart tablet structure and the device for charging tablets into the tank is complicated. Absent. Further, this document describes a color developing tablet using hydroxylamine as a preservative.However, this tablet is extremely weak to humidity, for example, the surface of the tablet absorbs moisture during the rainy season. A reaction occurs inside, and the storage and solubility deteriorate,
It was found that there was a disadvantage that sufficient photographic performance could not be obtained.

Thus, the present inventors have conducted various studies and found that the inclusion of a monosaccharide makes it possible to realize a solid processing agent comprising a part that solves the above problems.

[0013]

Accordingly, it is an object of the present invention to firstly improve the storage stability of the solid processing agent, secondly to improve the solubility of the solid processing agent, and thirdly to improve the solubility of the solid processing agent. A fourth object of the present invention is to provide a solid processing agent in which the generation of stain during photographic processing is prevented, and a fourth object is to provide a solid processing agent having improved photographic performance stability during processing. Another object of the present invention is to provide a silver halide color photographic light-sensitive material having improved social environment preservation, a solid color developing agent, and a method for processing a silver halide color photographic light-sensitive material using the processing agent.

[0014]

The constitution of the present invention which achieves the object of the present invention is as follows (1) to ( 11 ).

(1) At least one monosaccharide and paraffin
Silver halide containing nitryleneamine-based color developer
Solid color developer for color photographic light-sensitive materials,
The content of paraphenylenediamine color developer is weight ratio
% Or more, and the solid color developing agent
Does not contain a hydroxylamine salt .

(2) The solid color developing agent is in the form of a tablet,
The solid color developing agent according to the above (1), which is in the form of a granule or a powder.

(3) The solid color developing agent according to (1) or (2), wherein the solid color developing agent is in the form of a tablet.

(4) The solid color developing agent according to any one of (1) to (3), wherein the solid color developing agent comprises one agent.

(5) The above-mentioned paraphenylenediamine color development
The developer is 4-amino-N-ethyl-N- (β-methanesulfone
Midoethyl) -m-toluidine (sesquisulfate hydrate)
Rate) of (1) to (4),
Solid color development processing agent according to any one.

(6) At least one monosaccharide and paraffin
Silver halide containing nitryleneamine-based color developer
Solid color developer for color photographic light-sensitive materials,
The concentration when the solid color developing agent is dissolved as a working solution is
At least 1.5 × 10 ^-2 mol / l, and
The color developing agent does not contain hydroxylamine salt
A solid color developing agent.

(7) The solid color developing agent is in the form of a tablet,
The solid color developing agent according to the above (6), which is in any of a granular form and a powder form .

(8) The solid color developing agent is in the form of a tablet.
The solid color developing agent as described in (6) or (7) above .

(9) From one solid color developing agent
(6), (7) or
Is a solid color developing agent according to (8). (10) When the paraphenylenediamine-based color developer is 4-
Amino-N-ethyl-N- (β-methanesulfonamidoethyl
Le) -m-toluidine (sesquisulfate hydrate)
Any of (6) to (9) above,
Item 2. The solid color developing agent according to Item 1. (11) Imagewise exposure of silver halide color photographic materials
Later, in a method of continuous processing using an automatic developing machine,
When replenishing into the color developing tank, the above (1) to (9)
Color developing the solid color developing agent according to any one of the above.
It is characterized by being added and dissolved at the site that comes in contact with the processing solution
For processing silver halide color photographic light-sensitive materials.

By the way, certain saccharides are already known as preservatives (Japanese Patent Application Laid-Open No. 52-102727). However, when a solid processing agent having a color developing function is prepared, saccharides are contained. There is no suggestion that a solid processing agent which is resistant to humidity and excellent in solubility can be prepared.

The weight ratio of the color developing agent described in JP-A-52-102727 to the total capacity is less than 10%. In the present invention, the weight ratio of the color developing agent in the solid color developing agent is increased (10
% Or more) prevents rapid treatment and reduction of waste liquid, and has a different technical idea from the invention described in JP-A-52-102727.

Hereinafter, the above-mentioned saccharides will be described in detail.

[0027] (also referred to as carbohydrate) saccharide comprises monosaccharide and polysaccharide, many have the general formula C _n H _2n O _n. Monosaccharides generally refer to aldehydes or ketones of polyhydric alcohols and their reduced derivatives, oxidized derivatives, dehydrated derivatives, and a wide range of derivatives such as amino sugars and thio sugars. Alternatively, a polysaccharide refers to a product obtained by dehydrating and condensing two or more of the aforementioned monosaccharides.

Among these saccharides, more preferred are aldoses having a reducing aldehyde group and derivatives thereof, and particularly preferred are those corresponding to monosaccharides.

Specific examples of the monosaccharide that can be used in the present invention are shown below, but the present invention is not limited to these.

[0030] (1) Eritori preparative Lumpur (2) beta-D-arabinose (3) beta-L-arabinose (4) D-xylose (5) L-xylose (6) 2-deoxy-beta-D-ribose (7) α-D-lyxose (8) α-L-lyxose (9) D-ribose (10) L-ribose (11) L-arabitol (12) D-arabitol (13) ribitol (14) β-D -Altrose (15) β-L-altrose (16) β-D-allose (17) β-L-allose (18) α-D-galactose (19) β-D-galactose (20) α-L -Galactose (21) α-D-quinobose (22) α-D-glucose (23) β-D-glucose (24) β-D-lactose (25) Diquitalose (26) Diquitoxose (27) Shimarose (28) L -Soribose (29) D-tagatose (30) α-D-talose (31) 2-deoxy-D-glucose (32) α-D-fucose (33) -L-fucose (34) α-D-mannose (35) L-mannose (36) α-L-rhamnose (37) D-isositol (38) myo-inositol (39) galactitol (40) d-guercitol ( 41) D-curcitol (42) D-mannitol (43) L-iduronic acid (44) galactaric acid (45) α-D-galacturonic acid (46) D-glucaric acid (47) β-D-glucuronic acid (48 ) D-gluconic acid (49) L-gluconic acid (50) 2-deoxy-D-gluconic acid (51) D-mannuronic acid-6,3-lactone (52) Methyl = β-D-galactopyranoside ( 53) Methyl = α-D-galactopyranoside (54) Methyl = α-D-glucopyranoside (55) Methyl = β-D-glucopyranoside (56) Methyl = α-D-fructofuranoside (57) Methyl = α -D-mannopyranoside (58) Methyl = β-D-mannopyranoside (59) N-acetyl-α-D-galactosamine (60) N-acetyl-α-D-glucosamine (61) N-acetyl-α-D-mannosamine (62) Muramic acid (63) α-D-galactosamine (64) α-D-glucosamine (65) D- Masonosamine (66) D-glycero-α-galacto-heptose (67) D-glycero-β-L-manno-heptose (68) D-manno-heptulose (69) D-altro-3-heptulose (70) D- glycero-D-galacto-heptitol (71) D-glycero-D-talo-heptitol (72) D-erythro-D-galacto-octitol Monosaccharides are widely and naturally occurring, and commercially available products are easily available. For various derivatives, reduction, oxidation,
Alternatively, it can be easily synthesized by performing a dehydration reaction or the like.

The solid color developing agent of the present invention may be composed of one part containing all the components necessary for color developing of a silver halide color photographic light-sensitive material in one kind of solid. Preferred for handling operation. At this time, the compounds which are easily reacted among the components may be in a layered form separated by another compound or a film which is inactive to both.

The solid color developing agent of the present invention preferably contains substantially no hydroxylamine or a salt thereof, in order to more remarkably exhibit the effects of the present invention. However, the hydroxylamine derivative having a substituent is not limited to this.

The color developer contained in the solid color developer of the present invention is preferably a paraphenylenediamine color developer from the viewpoints of solubility and photographic processing performance. At this time,
It is preferable that the weight ratio of the color developing agent to the entire components is 10% or more, in order to realize another effect of the present invention, that is, low replenishment and low waste liquid, more preferably 12% or more, and even more preferably 15%. The above is particularly preferred.

As the paraphenylenediamine-based color developing agent, those having at least one hydrophilic group on an amino group or a benzene ring do not cause contamination of the photosensitive material.
In addition, it has the advantage of less irritation to the skin and is preferably used. Specific hydrophilic groups include

[0035]

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And the like.

Specific examples of color developing agents preferably used in the present invention include (C-1) to (C-16) described in Japanese Patent Application No. 2-203169, pp. 26-31. 61-2
Nos. (1) to (8) described on pages 89 to 31 of 89350 and (1) described on pages 5 to 9 of JP-A-3-246543.
To (26), and particularly preferred is Japanese Patent Application No. 2-203169.
Compounds (C-1), (C-
3), exemplified compound (2) described in JP-A-61-289350, and exemplified compound (1) described in JP-A-3-246543. The color developing agent is usually used in the form of a sulfate, a hydrochloride, a p-toluenesulfonate or the like. Among these paraphenylenediamine-based color developers, 4-amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline sesquisulfate monohydrate (CD-3) has a solubility in an alkaline solution. Particularly low, which has been an obstacle in realizing a reduction in the amount of waste liquid and a rapid development process by increasing the concentration of the replenisher, can be solved by directly replenishing the solid color developing agent of the present invention to the working solution. This is one of preferred embodiments of the present invention.

When the solid color developing agent of the present invention is dissolved as a working solution, the concentration of the paraphenylenediamine-based color developing agent is at least 1.5 × 10 ^-2 mol / l.
It is preferable from the viewpoint of rapid processing. Further, the color developing agents may be used alone or in combination of two or more kinds, and if desired, used in combination with a black and white developing agent such as phenidone, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone or methol. May be used.

Further, an auxiliary developer may be contained together with the developing agent. Examples of these auxiliary developers include known compounds such as metol, phenidone, N, N-diethyl-p-aminophenol hydrochloride, N, N, N ′, N′-tetramethyl-p-phenylenediamine hydrochloride, etc. Is contained.

Further, various additives such as a stain inhibitor, an anti-sludge agent, and a layering effect accelerator can be contained.

In the solid color developing agent according to the present invention,
A trace amount of sulfite can be contained as a preservative.
Examples of the sulfite include sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, and the like.

The solid color developing agent according to the present invention preferably contains a buffer. Examples of the buffer include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, disodium phosphate and tripotassium phosphate. , Disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borate), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-sulfo-2
And sodium 5-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).

The solid color developing agents according to the present invention include, as development accelerators, JP-B-37-16088, JP-B-37-5987 and JP-B-37-5987.
Nos. 8-7826, 44-12380, 45-9019 and U.S. Pat.
Thioether compounds represented by JP-A-13,247,
P-phenylenediamine compounds represented by 52-49829 and 50-15554, JP-B-44-30074, JP-A-50-13772
No.6, No.56-156826 and No.52-43429 4
Grade ammonium salts, U.S. Pat.Nos. 2,610,122 and 4,11
No. 9,462, p-aminophenols, U.S. Pat.
03, 3,128,182, 4,230,796, 3,253,919
No., JP-B-41-11431, U.S. Pat.Nos. 2,482,546, 2,591
Amine compounds described in 6,926 and 3,582,346 and the like,
JP-B-37-16088, JP-B-42-25201, U.S. Patent 3,128,183
No., JP-B-41-11431, JP-B-42-23883 and U.S. Pat.
Polyalkylene oxides represented by 2,501 and the like, 1-phenyl-3-pyrazolidones, hydrazines, mesoionic compounds, ionic compounds, imidazoles and the like can be contained as necessary.

In the present invention, chlorine ions, bromine ions and iodine ions can be added to the solid color forming agent for the purpose of preventing fog and the like.

The solid color developing agents of the present invention include a triazinylstilbene-based fluorescent whitening agent and Japanese Patent Application No. 2-240400.
A chelating agent represented by the general formula [K] described from page 69, below, line 9 to page 75 can be added. Further, the solid color developing agent may contain anionic, cationic, amphoteric or nonionic surfactants.

The bleaching agent preferably used in the bleaching agent or bleach-fixing agent according to the processing method of the present invention is represented by the following general formula [A]
Is a diiron complex salt of an organic acid represented by

[0047]

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In the above formula, A _{1 to} A ₄ may be the same or different and represent —CH ₂ OH, —COOM or —PO ₃ M ₁ M ₂ . M, M _1,
M ₂ represents a hydrogen atom, an alkali metal atom or an ammonium group, respectively. X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms.

The compound represented by formula (A) will be described below in detail.

In the above formula, A _{1 to} A ₄ are those described in Japanese Patent Application No. 1-260628.
Since they have the same meanings as A _{1 to} A ₄ described on page 12, line 15 to page 15, line 3, detailed description is omitted.

Preferred specific examples of the compound represented by the general formula [A] are shown below.

[0052]

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[0053]

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As the ferric complex salts of the compounds (A-1) to (A-12), sodium, potassium or ammonium salts of these ferric complex salts can be arbitrarily used. From the viewpoint of the effect and solubility of the object of the present invention,
Ammonium salts of these ferric complex salts are preferably used.

Among the above compound examples, those particularly preferably used in the present invention include (A-1), (A-3),
(A-4), (A-5) and (A-9), and particularly preferred is (A-1).

In the processing method of the present invention, as the bleaching agent or the bleach-fixing agent, besides the iron complex salt of the compound represented by the general formula [A], a ferric complex salt of the following compound can be used as a bleaching agent.

(A'-1) Ethylenediaminetetraacetic acid (A'-2) trans-1,2-cyclohexanediaminetetraacetic acid (A'-3) Dihydroxyethylglycidic acid (A'-4) Ethylenediamine terrakis methylene sulfone Acid (A'-5) Nitrilotrismethylenephosphonic acid (A'-6) Diethylenetriaminepentakismethylenephosphonic acid (A'-7) Diethylenetriaminepentaacetic acid (A'-8) Ethylenediamine diorthohydroxyphenylacetic acid (A'-9) ) Hydroxyethyl ethylenediamine triacetic acid (A'-10) Ethylenediaminedipropionic acid (A'-11) Ethylenediamineacetic acid (A'-12) Hydroxyethyliminodiacetic acid (A'-13) Nitrilotriacetic acid (A'-14) Nitrilo Tripropionic acid (A'-15) triethylenetetramine hexaacetic acid A'-16) Ethylenediaminetetrapropionic acid The amount of the ferric organic acid complex is preferably 0.1 to 2.0 mol, more preferably 0.15 to 1.5 mol / l, per liter of the bleaching solution or the bleach-fixing solution. Range.

Examples of the bleaching agent, bleach-fixing agent and fixing agent include indazole and derivatives thereof described in JP-A-64-295258 and compounds represented by formulas (I) to (IX) described in the same specification. In addition, by containing at least one of these exemplified compounds, an effect on rapidity can be obtained.

In addition to the above-mentioned accelerators, the exemplified compounds described on pages 51 to 115 of JP-A-62-123459 and pages 22 to 25 of JP-A-63-17445. And the compounds described in JP-A-53-95630 and JP-A-53-28426 can be used in the same manner.

The bleaching agent or the bleach-fixing agent may further contain a halide such as ammonium bromide, potassium bromide or sodium bromide, various optical brighteners, an antifoaming agent or a surfactant. it can.

As a fixing agent used as a fixing agent or a bleach-fixing agent in the processing method of the present invention, thiocyanates and thiosulfates are preferably used. The thiocyanate content is preferably at least 0.1 mol / l or more, more preferably 0.5 mol / l when processing a color negative film.
Mol / l or more, particularly preferably 1.0 mol / l or more. The thiosulfate content is preferably at least 0.2 mol / l or more, and more preferably 0.5 mol / l or more when a color negative film is processed. In the treatment method of the present invention, thiocyanate and thiosulfate can be used in combination.

The fixing agent or the bleach-fixing agent used in the processing method of the present invention may contain, alone or two or more kinds of pH buffers consisting of various salts, in addition to these fixing agents.
Further alkali halide or ammonium halide,
For example, it is desirable to contain a large amount of a rehalogenating agent such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide. Compounds known to be added to ordinary fixing agents or bleach-fixing agents, such as alkylamines and polyethylene oxides, can be added as appropriate.

A fixing agent or a bleach-fixing agent is disclosed in
It is preferable to add a compound represented by the following general formula [FA] described on page 56 of Japanese Patent No. 95258 and this exemplified compound, and not only exerts the effects of the present invention better, but also reduces a small amount of photosensitive material for a long period of time. Another effect is that the amount of sludge generated in the processing solution having a fixing ability when processing over a long period is extremely small.

[0064]

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The compound represented by the general formula [FA] described in the same specification is disclosed in US Pat. No. 3,335,161 and US Pat.
It can be synthesized by a general method as described in Japanese Patent No. 0,718. These compounds represented by the general formula [FA] may be used alone or in combination of two or more.

Good results can be obtained when the amount of the compound represented by the general formula [FA] is in the range of 0.1 to 200 g per liter of the processing solution.

In the treatment method of the present invention, the stabilizer preferably contains a chelating agent having a chelating stability constant for ferric ion of 8 or more. Here, the chelate stability constant is defined by LGSillen-AEMartell, “Sta
bility Constants of Metal-ion Complexes ”, The Che
mical Society, London (1964), S. Chaberek / AEMart
ell, “Organic Sequestering Agants”, Willey (19
59) means a constant generally known by

As chelating agents having a chelate stability constant for ferric ion of 8 or more, Japanese Patent Application No. 2-234776,
No. 1-324507 and the like.

The above chelating agent is used in an amount of 1 liter of the stabilizing solution.
Good results are obtained in the range of preferably 0.01 to 50 g, more preferably 0.05 to 20 g.

Preferred compounds to be added to the stabilizer include ammonium compounds. These are supplied by ammonium salts of various inorganic compounds. The addition amount of the ammonium compound is 0.001 to 1.0 per 1 liter of the stable number.
The molar range is preferred, more preferably in the range of 0.002 to 2.0 moles. Further, the stabilizer preferably contains a sulfite.

Further, the stabilizer preferably contains a metal salt in combination with the chelating agent. As such metal salts, Ba, Ca, Ce, Co, In, La, Mn, Ni, Bi, Pb,
There are metal salts of Sn, Ti, Zr, Mg, Al or Sr, which can be supplied as inorganic salts such as halides, hydroxides, sulfates, carbonates, phosphates, acetates or water-soluble chelating agents. The amount used is preferably in the range of 1 × 10 ^-4 to 1 × 10 ^-1 mol, more preferably in the range of 4 × 10 ^-4 to 2 × 10 ^-2 mol per liter of the stabilizing solution.

As the stabilizer, an organic acid salt (citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid, etc.), a pH adjuster (phosphate, borate, hydrochloric acid, sulfate, etc.) are added. can do. In the present invention, known shock-absorbing agents can be used alone or in combination as long as the effects of the present invention are not impaired.

Next, the photosensitive material to which the solid color developing agent of the present invention is applied will be described.

When the light-sensitive material is a photographic light-sensitive material, silver iodobromide or silver iodobromochloride having an average silver iodide content of 3 mol% or more is used as silver halide grains.
Silver iodobromide containing from 15 mol% to 15 mol% of silver iodide is preferred. Among them, the average silver iodide content preferred in the present invention is from 5 mol% to 12 mol%, most preferably from 8 mol% to 11 mol%.

In the light-sensitive material processed with the solid color developing agent of the present invention, as the silver halide emulsion, those described in Research Disclosure 308119 (hereinafter abbreviated as RD308119) can be used. The places to be described are shown below.

[Item] [RD308119] Iodine composition 993 IA Item Manufacturing method 993 IA and 994 E Crystal habit Normal crystal 993 IA item Twin Twin 晶 Epitaxial 〃 Halogen composition uniform 993 I- Item B Not uniform 一 様 Halogen conversion 994 I-C item 項 Substitution 〃 Metal-containing 994 I-D item Monodisperse 995 I-F item Solvent addition 潜 Latent image formation position Surface 995 I-G item Internal 内部 Applicable photosensitive material negative 995 Item IH Positive (including internal fog particles) 用 い る Use a mixture of emulsions 995 IJ Desalination 995 II-A Silver halide emulsions that have been subjected to physical ripening, chemical ripening and spectral sensitization use. Additives used in such a process are described in Research Disclosure No. 17643, No. 187
No. 16 and No. 308119 (hereinafter RD17643 and RD1871 respectively)
6 and RD308119).

The places to be described are shown below.

[Item] [Page of RD308119] [RD17643] [RD18716] Chemical sensitizer Section 996 III-A 23 648 Spectral sensitizer 996 IV-AA, B, C, D, E, H, I, J Section 23-24 648-9 Supersensitizer 966 IV-AE, Section J 23-24 648-9 Antifoggant 998 IV 24-25 649 Stabilizer 998 VI 24-25 649 It is described in Roja. The relevant sections are described below.

[Item] [Page of RD308119] [RD17643] [RD18716] Anti-turbidity agent 1002 VII-I 25 650 Dye image stabilizer 1001 VII-J 25 Whitening agent 998 V 24 UV absorber 1003 VIII C , VIII C 25-26 Light absorber 1003 VIII 25-26 Light scattering agent 1003 VIII Filter dye 1003 VIII 25-26 Binder 1003 IX 26 651 Static inhibitor 1006 VIII 27 650 Hardener 1004 X 26 651 Plasticizer 1006 XII 27 650 Lubricant 1006 XII 27 650 Activator / Coating aid 1005 XI 26-27 650 Matting agent 1007 XVI Developer (contained in photosensitive material) Item 1011 XX-B Processed in the solid color developing process of the present invention Various couplers can be used in the light-sensitive material, and specific examples are described in the above-mentioned Research Disclosure. The relevant sections are described below.

[Item] [RD308119] [RD17643] [RD18716] Yellow coupler 1001 VII-D VIIC-G Magenta coupler 1001 VII-D VIIC-G Cyan coupler 1001 VII-D VIIC -G DIR coupler 1001 VII-F VII F BAR coupler 1002 VII-F Other useful residue releasing coupler 1001 VII-F Alkali soluble coupler 1001 VII-E Additives are described in RD308119 XIV. Can be added by a conventional dispersion method.

In the present invention, RD17643 No. 28
The support described in pages RD18716, pages 647 to 648 and RD308119, XIX can be used.

The light-sensitive material can be provided with an auxiliary layer such as a filter layer or an intermediate layer described in the aforementioned RD308119 VII-K. The photosensitive material is RD308119 VII described above.
Various layer configurations such as a normal layer, a reverse layer, and a unit configuration described in the section -K can be adopted.

Next, a preferred photosensitive material for printing to which the solid color developing agent according to the present invention is applied will be described.

As the silver halide grains in the light-sensitive material, silver chloride-based silver halide grains containing at least 80 mol% or more of silver chloride are used, preferably 90 mol% or more.
Particularly preferably, those containing 95 mol% or more, most preferably 99 mol% or more are used.

The silver chloride emulsion mainly composed of silver chloride can contain silver bromide and / or silver iodide as a silver halide composition in addition to silver chloride. In this case, the silver bromide content is 20 mol% or less. Is preferably 10 mol% or less, more preferably 3 mol% or less, and when silver iodide is present, it is preferably 1 mol% or less, more preferably 0.5 mol%.
Hereinafter, it is most preferably zero. Such silver chloride 50
Silver halide grains mainly composed of silver chloride consisting of at least
It may be applied to at least one silver halide emulsion layer, but is preferably applied to all photosensitive silver halide emulsion layers.

The crystal of the silver halide grains may be a normal crystal, a twin crystal or other crystal, and may have [1.0.0] plane and [1.1.
1] Any ratio of planes can be used. Furthermore, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may be a layer (phase) -like structure (core-shell type) in which the inside and the outside are different. Good. These silver halides may be of a type in which a latent image is mainly formed on the surface or of a type in which a latent image is formed inside a grain. Furthermore, tabular silver halide grains (JP-A-58-113934)
No., Japanese Patent Application No. 59-170070) can also be used.
Further, silver halides described in JP-A Nos. 64-26837, 64-26838 and 64-77047 can be used.

Further, the silver halide grains may be prepared by an acid method,
It may be obtained by any preparation method such as a neutral method or an ammonia method.

Further, for example, a method may be used in which seed particles are formed by an acidic method, and further grown by an ammonia method having a high growth rate to a predetermined size. When growing silver halide grains, controlling the pH, pAg, etc. in the reaction vessel, for example, an amount of silver ion corresponding to the growth rate of silver halide grains as described in JP-A-54-48521. And halide ions are preferably sequentially and simultaneously injected and mixed.

The red-sensitive layer of the silver halide emulsion layer of the light-sensitive material processed by the solid color developing agent according to the present invention may be, for example, a non-diffusible color coupler for forming a zion partial color image, generally phenol or α-naphthol. A system coupler can be contained. The green-sensitive layer can include, for example, at least one non-diffusible color coupler that produces a magenta partial color image, usually a 5-pyrazolone-based color coupler and a pyrazolotriazole.
The blue-sensitive layer can include, for example, at least one non-diffusing color coupler that produces a yellow partial color image, generally a coupler having an open chain ketomethylene group. The color coupler can be, for example, a 6, 4 or 2 equivalent coupler.

In the light-sensitive material to which the solid color developing agent of the present invention is applied, a 2-equivalent coupler is particularly preferable.

Suitable couplers are disclosed, for example, in the following publications: Agfa's work report (Mitteilunglnausden)
Forschungslaboratorien der Agfa), Leverkusen / Munchen, Vol. II
I. p. 111 (1961) "Color coupler" (Farbkuppler) by W. Pelz; K. Venkataraman, "The chemistry of synthetic soybeans" (The Chemisry of
Synthetic Dyes), Vol.4, 341-387, Academic Press, "The Theory of the.
Photographic Process ”(The Theory of the
Photographic Process), 4th edition, pages 353-362; and Research Disclosure No. 1
7643, section VII.

In the light-sensitive material to which the solid color developing agent of the present invention is applied, in particular, magenta represented by the general formula [M-1] as described on page 26 of JP-A-63-106655. Couplers (Examples of these magenta couplers include those described in JP-A-63-106655, pages 29 to 34, and
o.1 to No.77. ), A cyan coupler represented by the general formula [C-I] or [C-II] also described on page 34 (specific examples of cyan couplers include (C) described in the same specification, pages 37 to 42). '-1) to (C'-82),
(C "-1) to (C" -36)), and 20
It is preferable to use high-speed yellow couplers described on the page (specific examples of yellow couplers include (Y'-1) to (Y'-39) described in the same specification, 21 to 26).

In the present invention, the method for replenishing the color developing tank for continuous processing using an automatic developing machine after imagewise exposing the silver halide color photographic light-sensitive material is as follows. It is preferable to dissolve it by adding it to a dissolving portion provided at a site that comes into contact with the color developing solution.

That is, the self-developing machine preferably used in the present invention comprises a processing tank (main tank) for processing a silver halide color photographic light-sensitive material and a dissolving section (sub-tank) for dissolving a solid processing agent. The processing tank and the dissolving section are in communication with each other, and the liquid is circulated between the processing tank and the dissolving section by having a circulating means.
It is preferable that the dissolving section has a furnace passage means for preventing impurities, insoluble matter or undissolved matter mixed in the supplied solid processing agent from flowing into the processing tank.

Further, when the solid processing agent is introduced into the dissolving section, it is a preferable embodiment for carrying out the present invention to replenish water with a minimum evaporation. That is, if the processing liquid tank at a certain temperature always evaporates and the water is not replenished, the liquid level will decrease and become thicker, and as a result, deterioration of photographic performance, projection, tar, etc. will be a problem. . Therefore, a minimum amount of water supply for maintaining the tank liquid level is required.

In addition, it is necessary to consider taking out of the photosensitive material in addition to the amount of water to be replenished. In particular, it is necessary to supply water to the color developing tank in consideration of taking out of the photosensitive material other than the amount of evaporation. However, if the replenishment is too much, there is a problem that the effect of the present invention is not preferable and the amount of waste liquid increases. Therefore, in a preferred embodiment of the present invention, the water supply amount is set so that the overflow amount is 5% or less, preferably 3% or less with respect to the processing tank.

The self-developing machine has a detecting means for detecting a processing amount of the silver halide color photographic light-sensitive material, a supply device for automatically supplying a solid processing agent to the dissolving section according to the processing amount, and a water supply device. It is preferable to have a rehydration device for replenishment.

In the present invention, a processing section for processing a photographic material and a dissolving section for dissolving a solid photographic processing agent are provided, and the dissolving section is arranged at a portion of the processing section which comes into contact with the processing solution; By using an automatic developing machine having a dissolving means, it is possible to substantially eliminate the manual dissolving work conventionally performed, and furthermore, a replenishing tank or a replenishing solution which occupies about half of the automatic developing machine. It is even possible to eliminate pumps for use, and it is possible to greatly reduce costs and downsize equipment and devices. In addition, since the dissolving unit has a dissolving means in the dissolving part, even a solid photographic processing agent dissolves promptly, preventing a local increase in concentration and making it uniform throughout the processing part.

When there is no dissolving part, for example, when granules are added to a tablet directly in a tank treatment tank or a replenishing tank, although the initial solubility is slightly good, the dissolution rate is slow, and the alkali agent and the like are hardened and hardly dissolved. In addition, since it is deposited on the bottom of the tank, local concentration of the photographic processing agent may be locally increased, and tar and insoluble substances may be generated, which seriously affects photographic performance and clogging of the circulation system.

Further, in the present invention, since the photographic processing agent is a solid processing agent, the parts agent is scattered during the work, and the human body,
In particular, it is possible to supply an environmentally compatible treatment agent that does not adhere to or contaminate hands, clothes, and peripheral devices, and does not require the use of plastic bottles.

Further, by providing the processing agent supply means in the dissolving section of the automatic developing machine, there is no need to manually input the processing agent into the dissolving section, and the working efficiency is greatly improved.

[0102]

【Example】

Example 1 A processed tablet for a color negative film was prepared according to the following operation.

Tablet for replenishing color development for color negative Operation (1) CD-4 [4-amino-3-methyl-N-ethyl-β-
(Hydroxy) ethylaniline sulfate] 65 g is pulverized in an air jet pulverizer until the average particle size becomes 10 μm.
This fine powder is placed in a commercial fluidized bed spray granulator at room temperature for about 8 hours.
After granulating by spraying 5.0 ml of water for minutes, the granules are dried at 60 ° C. for 10 minutes. Next, the granulated material is vacuumed at 40 ° C.
For 2 hours to remove the moisture of the granules almost completely.

Operation (2) Preservatives shown in Table 1 (monosaccharides, comparative compounds, and monosaccharides are indicated by exemplified compound numbers. The same applies to the following examples.)
0.46 mol is pulverized and granulated in the same manner as in the operation (1). The spray amount of water is 2.6 ml, and after granulation, it is dried at 60 ° C. for 7 minutes. Next, the granules are dried at 40 ° C. for 2 hours in a vacuum to remove the moisture of the granules almost completely.

Operation (3) 58 g of sodium sulfite, 380 g of potassium carbonate, 3 g of sodium hydrogen carbonate, 4 g of sodium bromide, and 25 g of diethylenetriaminepentaacetic acid were ground in the same manner as in (1), and then uniformly mixed with a commercially available mixer. Next, in the same manner as in (1), granulation is performed with the spray amount of water set to 200 ml. After granulation, granulate at 65 ℃
And then dry the granules in vacuo at 40 ° C. for 2 hours to remove almost completely the moisture of the granules.

Operation (4) The granules prepared in the above operations (1) to (3) are uniformly mixed for 10 minutes using a mixer in a room conditioned at 25 ° C. and a relative humidity of 40% or less. Next, the mixture was subjected to compression tableting using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho to produce 100 color developing color replenishing tablets for color negative.

Each of the obtained tablet samples was put in a polyethylene bag, and each was sealed and sealed at 70 ° C. and 80% relative humidity.
Stored for months. The appearance of the tablets after storage was visually observed. Further, the solubility of each of the four samples after storage in 500 ml of water was evaluated. Further, the amount of the color developing agent after storage was measured, and the residual ratio to the sample before storage was determined.

The appearance of the tablets after storage was evaluated according to the following criteria.

◎: Deformation of the shape of the tablet and little change in color were not observed. 着色: The color of the tablet was slightly dark, but the shape of the tablet was hardly deformed. Δ: The color of the tablet was slightly dark, and the shape of the tablet was also poor. X: Colored black, deliquescent and tablet disintegrated. The solubility was evaluated according to the following criteria.

A: Immediately dissolved and completely dissolved without stirring. A: Dissolved gradually and dissolved within 1 hour without stirring. Δ: Dissolved gradually, but a solid remained. The substance was finally dissolved by stirring. X: The substance was gradually dissolved, but a solid remained, and the substance remained dissolved even after stirring. Tables 1 and 2 show the results.

[0111]

[Table 1]

[0112]

[Table 2]

From Tables 1 and 2, it can be seen that the solid color developing agent using the preservative of the present invention shows good preservability and excellent solubility.

Example 2 A color paper treating agent was prepared according to the following procedure.

Replenishing tablet for color development for color paper Operation (A) CD-3 [4-amino-3-methyl-N-ethyl-N-N-
100 g of [β- (methanesulfonamido) ethyl] aniline sulfate] is pulverized in an air jet pulverizer until the average particle size becomes 10 μm. After granulating the fine powder by spraying 4.0 ml of water at room temperature for about 5 minutes in a commercially available fluidized bed spray granulator, the granulated product is dried at 60 ° C. for 10 minutes. Next, the granules are dried at 40 ° C. for 2 hours in a vacuum to remove the moisture of the granules almost completely.

Operation (B) 0.41 mol of the compounds shown in Tables 3 and 4 are ground and granulated in the same manner as in Operation (A). Spray volume of water is 3.0ml, after granulation, 60
Dry at ℃ for 10 minutes. Next, the granulated material is vacuumed at 40 ° C. for 2 hours.
After drying for a time, the water content of the granules is almost completely removed.

Operation (C) 30 g of Tinopearl SFP (manufactured by Ciba Geigy), 2.0 g of sodium sulfite, 400 g of potassium carbonate, 0.5 g of potassium bromide, 30 g of dicatylenetriamine pentaacetic acid, 200 g of polyethylene glycol (average molecular weight 6000), 200 g of potassium hydroxide After pulverizing 15 g in the same manner as in (A), the mixture is uniformly mixed with a commercially available mixer. Next, in the same manner as in (A), granulation is performed with a water spray amount of 200 ml. After granulation, the granules are dried at 65 ° C. for 15 minutes, and then the granules are dried in vacuum at 40 ° C. for 2 hours to almost completely remove moisture from the granules.

Operation (D) The granules prepared in the above operations (A) to (C) are uniformly mixed for 10 minutes using a mixer in a room conditioned at 25 ° C. and a relative humidity of 40% or less. Next, the mixture was subjected to compression tableting using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho to produce 100 color developing and replenishing tablets for color paper.

[0119] Five of the obtained tablet samples were put in a polyethylene bag and hermetically sealed, and then placed at 70 ° C and a relative humidity of 80%.
Stored for months. The tablet sample after storage was evaluated in the same manner as in Example 1. The evaluation criteria are the same as in the first embodiment.
The results are shown in Tables 3 and 4.

[0120]

[Table 3]

[0121]

[Table 4]

From Tables 3 and 4, it can be seen that the solid color developing agent using the preservative of the present invention has good storage stability and excellent solubility.

Example 3 Tableting was performed in the same manner as in Example 1 except that the weight ratio of the developing agent CD-4 in the tablet was changed as shown in Tables 5 to 6, and 100 tablets of color negative were developed. A developed tablet was prepared. Each of the obtained tablet samples was sealed in a bag of five polyethylene samples and stored at 65 ° C. and 70% relative humidity for 4 weeks. The tablet sample after storage was evaluated in the same manner as in Example 1. The evaluation criteria are the same as in Example 1. Table 5 shows the results.
It is shown in Table 6.

[0124]

[Table 5]

[0125]

[Table 6]

From Tables 5 and 6, as the content of the color developing agent increases, the preservability and solubility of the comparative sample deteriorate, whereas the tablet sample of the present invention has good preservability and solubility. It can be seen that is maintained.

Example 4 Tableting was performed in the same manner as in Example 1 except that the weight ratio of the developing agent CD-3 in the tablet was changed as shown in Tables 7 and 8, and 100 tablets of color negative were developed. A developed tablet was prepared. Each of the obtained tablet samples was sealed in a bag of five polyethylene samples and stored at 65 ° C. and 70% relative humidity for 4 weeks. The tablet sample after storage was evaluated in the same manner as in Example 1. The evaluation criteria are the same as in Example 1. Table 7-
It is shown in Table 8.

[0128]

[Table 7]

[0129]

[Table 8]

From Tables 7 and 8, it can be seen that as the content of the color developing agent increases, the preservability and solubility of the comparative sample deteriorate, whereas the tablet sample of the present invention has good preservability and solubility. It can be seen that is maintained.

Example 5 The following four color negative color developing and replenishing processing agents were prepared.

Processing agent for replenishing color development (i) Preservative shown in Table 9 0.05 mol 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate (CD-4) 6.5 g Part A shall be 6 g or more of sodium sulfite.

Potassium carbonate 38 g Sodium bicarbonate 0.3 g Sodium bromide 0.4 g Diethylenetriaminepentaacetic acid 2.5 g or more shall be B part.

The above materials were divided into A part and B part, each of which was dissolved in water and finished to 500 ml (see “2
Part A), and a material prepared by dissolving all the materials in water and finishing to 1 l without dividing the A and B parts (described as “1 part configuration” in Table 9).

Processing agent for replenishing color development (ii) Preservative described in Table 9 0.025 mol 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate (CD-4) 3.3 g Part A is 3 g or more of sodium sulfite.

Potassium carbonate 19 g Sodium bicarbonate 0.15 g Sodium bromide 0.2 g Diethylenetriaminepentaacetic acid 2.5 g or more is defined as Part B.

The above material was divided into A part and B part, each of which was placed in a polyethylene bag in powder form (Table 9).
In the table, “Part 2” is used, and A and B parts are not divided, and all materials are mixed in powder form and placed in a polyethylene bag (referred to as “1 part” in Table 9). .

Color developing and replenishing processing agent (iii) Using the same material as the color developing and replenishing processing agent (ii),
A part and a B part are each granulated and granulated, and each is put in a polyethylene bag (referred to as “two-part composition” in Table 9). The mixture is granulated, granulated, and placed in a polyethylene bag (referred to as “one-part composition” in Table 9).

Processing agent for color development replenishment (iv) Using the same material as the processing agent for color development replenishment (ii),
Each tablet was divided into a part and a B part, and five tablets were prepared, each of which was put in a polyethylene bag (described as “two-part composition” in Table 9). The tablets are mixed uniformly to form five tablets, which are placed in a polyethylene bag (referred to as "one-part composition" in Table 9).

The above processing agent for color development replenishment was stored at 65 ° C. and a relative temperature of 70% for 4 weeks, and each sample after storage was evaluated in the same manner as in Example 1. Table 9 shows the results.

In Table 9, the meanings of the symbols in the column of appearance evaluation are as follows.

◎: No change in appearance was observed. ○: Slightly brown colored. △: Pretty black colored. X: Tar-like black material was observed. Solubility evaluation was the same as in Example 1. Evaluation criteria were used.

[0143]

[Table 9]

As is clear from Table 9, when the preservative of the present invention was used, the processing agent for replenishing color development was in the form of a tablet,
Preservability and solubility are greatly improved in the case of granules and powders. Particularly when the processing agent is in the form of tablets, excellent preservability and solubility can be maintained even in a one-part configuration. Becomes

Example 6 Four color developing agents for color paper shown below were prepared.

Processing agent for replenishing color development (i ') Preservative described in Table 10 0.04 mol 4-amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline sesquisulfate monohydrate (CD- 3) 10 g Sodium sulfite 0.2 g Tinopearl SFP (manufactured by Ciba Geigy) 3 g or more shall be Part A.

Potassium carbon 40 g Diethylenetriaminepentaacetic acid 3 g Potassium bromide 0.05 g Polyethylene glycol (average molecular weight: 6000) 20 g or more is defined as B part.

The above material was divided into A part and B part, each of which was dissolved in water and finished to 500 ml (see “2
A part which is not divided into A and B parts, but is prepared by dissolving all the materials in water and finishing to 1 l (referred to as "one part constitution" in Table 10).

Processing agent for replenishing color development (ii ') Preservative described in Table 10 0.02 mol 4-amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline sesquisulfate monohydrate (CD- 3) 5 g Sodium sulfite 0.1 g Tinopearl SFP (manufactured by Ciba-Geigy) 1.5 g or more shall be Part A.

Potassium carbonate 20 g Diethylenetriaminepentaacetic acid 1.5 g Potassium bromide 0.025 g Polyethylene glycol (average molecular weight: 6000) 10 g or more is defined as B part.

The above material was divided into A part and B part, each of which was placed in a polyethylene bag as powder (Table 6).
(Indicate “two-part configuration” in Table 10), prepare a mixture of all materials in powder form without mixing A and B parts and place in a polyethylene bag (described as “one-part configuration” in Table 10). .

Processing agent for color development replenishment (iii ') Using the same material as the above-mentioned processing agent for color development replenishment (ii'), divided into A part and B part, each of which is granulated into granules, In a polyethylene bag (Table 2 "2
Parts are not divided into A and B parts. All materials are uniformly mixed, granulated, granulated and placed in a polyethylene bag (referred to as "1 part composition" in Table 10). ) Is prepared.

Processing agent for color development replenishment (iv ') Using the same material as the processing agent for color development replenishment (ii'), five tablets were prepared for each of A part and B part, In a polyethylene bag (described as “two-part composition” in Table 10), A and B parts are not divided.
All the ingredients are uniformly mixed to form five tablets, which are placed in a polyethylene bag (referred to as "one-part composition" in Table 10).

The above processing agent for replenishing color development was stored at 65 ° C. and a relative temperature of 70% for 4 weeks, and each sample after storage was evaluated in the same manner as in Example 1. Table 10 shows the results.

In Table 10, the evaluation criteria for the appearance evaluation and the dissolution evaluation are the same as in Example 5.

[0156]

[Table 10]

As is clear from Table 10, when the preservative of the present invention was used, the processing agent for replenishing color development was in the form of a tablet,
Preservability and solubility are greatly improved in the case of granules and powders. Particularly when the processing agent is in the form of tablets, excellent preservability and solubility can be maintained even in a one-part configuration. Becomes

Example 7 A color developing replenisher having the following composition was prepared.

Exemplified Compound (9) 5.9 g Developing agent shown in Table 11 (See Table 11) Sodium sulfite 0.2 g Potassium carbonate 40 g Tinopearl SFP (manufactured by Ciba Geigy) 3.0 g Diethylenetriaminepentaacetic acid 3.0 g Potassium bromide 0.05 g Polyethylene glycol ( Average molecular weight: 6000) 20 g Potassium hydroxide 1 g These were dissolved in water to make 1 liter, and the pH was adjusted to 10.6 with sulfuric acid or aqueous potassium hydroxide solution.

Separately, tablets having the same composition as described above were tabletted in the same manner as in Example 2 to prepare 10 tablets for color development replenishment. Each of the color developing replenishers was placed in a 1-liter beaker and stored at room temperature while being opened. On the other hand, five tablet samples were left at room temperature. One week later, the state of the color developing replenisher was observed. In addition, the residual ratio of both developing agents was measured. In the case where the replenishment solution caused precipitation, the supernatant was collected and the concentration of the developing agent was measured.

The condition of the replenisher was evaluated according to the following criteria.

：: No precipitate was observed, and the solution was slightly colored. Δ: No precipitate was observed, but the solution was considerably colored. X: A crystalline precipitate was observed. Are shown in Table 11.

[0163]

[Table 11]

From Table 11, it is found that 4-amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) is used as a developing agent.
Aniline sesquisulfate monohydrate (CD-
When 3) is used at a high concentration, precipitation occurs in the conventional solution replenishment method, and it can be seen that a constant concentration of the main drug cannot be maintained. When CD-3 is used as a developing agent, multiple replenishments are required, resulting in a large amount of waste liquid. By putting the solid processing agent of the present invention directly into the working liquid,
Dissolved water required for conventional replenishment can be greatly reduced. The effect is more remarkable when CD-3 having low solubility is used as a color developer.

Example 8 A sample described in Japanese Patent Application No. 2-234777 was exposed to light by a conventional method, and a running test was performed using the following automatic developing machine and processing agent.

Automatic developing machine Konica Color Negative Film Processor CL-KP-50
The QA was equipped with a tablet supply function, liquid level detection function, hot water supply function, etc. by remodeling, and processing experiments were performed.

FIG. 1 is a schematic explanatory view showing an example of a self-developing machine according to the present invention, which simply shows a control mechanism of a processing apparatus for a color negative film.

When the color negative film is carried in from the photosensitive material insertion section 13 and passes through the photosensitive material area detecting sensor 7 and a certain amount of area is detected, the replenishing agent replenishing device 8, the replenishing water replenishing device 10, and the electromagnetic The valve 12 operates in response to a signal from the control unit 11, and the replenishing agent and the replenishing water for liquid preparation are replenished to the respective processing tanks 1, 2, 3, and 5 in required amounts.

Also, if the temperature of the automatic machine is adjusted for several hours,
When the processing liquid 17 in each of the processing tanks 1 to 5 evaporates and falls below a certain liquid level, the liquid level detection sensor 9 operates, and upon receiving a signal from the control unit 11, the replenishing water replenishing device 10 and the solenoid valve 12 are operated. Then, the replenishment water for evaporation correction is supplied until the upper limit detection mechanism of the liquid level detection sensor 9 operates. It is preferable that the temperature of the washing hot water 14, which is the replenishing water supplied by the replenishing water replenishing pipe 15, be adjusted for both the replenishing water for adjusting liquid and the replenishing water for evaporating correction. Each of the processing tanks 1 to 5 has a color developing tank 1, 2
Denotes a bleaching tank, 3 denotes a fixing tank, 4 denotes a washing tank, and 5 denotes a stabilizing tank. 6 is a drying section.

FIG. 2 is a schematic explanatory view showing an example of the replenishing agent replenishing device 18 in the case where a solidified tablet is used as the replenishing agent.

When the control section 11 receives a signal from the photosensitive material area detecting sensor 7 and the solid replenishing agent replenishing cam 22 is operated, the solid replenishing agent pushing claw 23 is turned into a solid replenishing cartridge housed in the cartridge 25. The treatment agent 24 is added to each of the treatment tanks 1, 2, 3,
Filtration device in sub-tank 20, which is the replenishment treatment agent dissolving section
Replenish one or several pieces inside 21. The replenished solid replenishing agent 24 gradually dissolves and is supplied to the main processing tank 16 of each of the processing tanks 1, 2, 3, and 5 by the circulation pump 18. If the circulation pump 18 is configured so that all or most of the circulating flow of the processing liquid 17 circulating between the main processing tank 16 and the sub-tank 20 directly passes through the filtration device 21 in the sub-tank 20, the replenishing processing agent 24 Will be more soluble. In the drawing, 19 is a temperature control heater, 26 is a pressing spring for pressing and holding the replenishing agent 24 in the cartridge 25, and 27 is a main processing tank 16 of each of the processing tanks 1, 2, 3, and 5.
A communication pipe between the tank and the sub tank 20, a processing rack 28, and an overflow port 29.

FIG. 3 is a schematic explanatory view showing an example of the replenishing water supply section. In FIG. 3, as in FIG. 2, the replenishing agent 24 is a solidified tablet.

In response to the signal from the photosensitive material area detecting sensor 7, the control section 11 operates to operate the solid replenishing agent replenishing cam 22 and the solid replenishing agent pushing claw 23 to replenish the solid replenishing agent 24 at the same time. The replenishing water supply device 10 and the solenoid valve 12 operate,
Replenishment water for replenishment is replenished. The replenishment amount of the replenisher water for preparation is
The problem can be solved by inputting the operation time of the solenoid valve 12 and the replenishing water replenishing device 10 to the control unit 11 in advance to the amount necessary for dissolving the replenishing agent 24.

When the liquid level of the processing liquid 17 in the processing tanks 1 to 5 is lowered due to evaporation during the temperature control or stoppage of the automatic developing machine, the liquid level detecting sensor 9 detects the lowered liquid level. A signal is transmitted to the control unit 11, and the solenoid valve 12 and the replenishing water replenishing device 10 are operated to replenish the evaporation correcting replenishing water to a normal liquid level. When the liquid level reaches the regular liquid level, the liquid level detection sensor 9 detects the regular liquid level, transmits a signal to the control unit 11, and outputs the signal to the solenoid valve 12.
Then, the operation of the replenishing water supply device 10 is stopped.

The standard processing conditions of the automatic processing machine are shown below.

Processing Step Temperature Time Color development 38 ± 0.3 ° C. 3 minutes 15 seconds Bleaching 38 ± 1.0 ° C. 45 seconds Fix-1 38 ± 1.0 ° C. 45 seconds Fix-2 38 ± 1.0 ° C. 45 seconds Stable-1 38 ± 3.0 ° C. 20 seconds Stable-2 38 ± 3.0 ℃ 20 seconds Stable-3 38 ± 3.0 ℃ 20 seconds Drying 60 ℃ 60 seconds The stabilizer is replenished to the third tank, and the overflow liquid flows into the second and first tanks sequentially. System.

Replenishing tablets used Color developing replenishing tablets 1600 color negative color developing replenishing tablets for color negative were obtained by repeating the same operation as in Example 1 except that the preservative was changed as shown in Table 12. It was created.

Tablets for replenishing bleach for color negatives Operation (5) 1,3-propanediaminetetraacetic acid ferric potassium monohydrate 237
g, 60 g of succinic acid, 73 g of maleic acid, and 10 g of 1,3-propanediaminetetraacetic acid are pulverized and granulated in the same manner as in the operation (1). The spray amount of water is 5.0 ml, and after granulation, it is dried at 60 ° C. for 7 minutes. Next, the granules are dried at 40 ° C. for 2 hours in a vacuum to remove the moisture of the granules almost completely.

Operation (6) 100 g of sodium nitrate, 60 g of potassium bromide and 60 g of potassium carbonate are ground and granulated in the same manner as in the operation (1). The spray amount of water is 1.0 ml, and after granulation, it is dried at 70 ° C. for 3 minutes. Next, the granules are dried at 40 ° C. for 2 hours in a vacuum to remove the moisture of the granules almost completely.

Operation (7) The granules prepared in the above operations (5) and (6) are uniformly mixed for 10 minutes using a mixer in a room conditioned at 25 ° C. and a relative humidity of 40% or less. Next, the mixture was subjected to compression tableting repeatedly using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho, with the filling amount per tablet being 6.0 g, to produce 80 color negative bleaching replenishing tablets.

This operation was repeated to produce 1500 tablets.

Fixation replenishing tablet for color negative Operation (8) 950 g of potassium thiosulfate, sodium thiocyanate 2020
g, 120 g of sodium sulfite, 150 g of potassium carbonate, and 10 g of disodium ethylenediaminetetraacetate are pulverized and granulated in the same manner as in the operation (1). The spray amount of water is 30 ml, and after granulation, it is dried at 60 ° C. for 60 minutes. Next, the granulated material is vacuumed at 40 ° C.
For 8 hours to remove the water content of the granules almost completely.

Operation (9) The granulated product prepared in the above operation (8) was subjected to a reaction at 25 ° C. and a relative humidity of 40%.
Mix uniformly for 10 minutes using a mixer in a humidified room below. Next, the mixture was filled into tablets using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho.
The compression tableting was repeated at 13.0 g, and 200 bleach replenishing tablets for color negative were prepared.

This operation was repeated to prepare 1000 tablets.

Tablet for stable replenishment for color negative Operation (10) 200 g of m-hydroxybenzaldehyde, Emulgen 985;
10 g and 45 g of potassium carbonate are ground and granulated in the same manner as in the operation (1). The spray amount of water is 3.0 ml, and after granulation, the granules are dried in vacuum at 30 ° C. for 8 hours to almost completely remove water from the granules.

Operation (11) The granulated product prepared in the above operation (10) was subjected to a reaction at 25 ° C and a relative humidity of 40%.
Mix uniformly for 10 minutes using a mixer in a humidified room below. Next, the mixture was filled into tablets using a tableting machine modified from Kikusui Seisakusho's Tough Press Cort 1527HU.
The compression tableting was repeated at 0.2 g, and a required amount of a stable replenishment tablet for color negative was prepared.

Processing tank liquid to be used Color developing tank liquid (21.0 liters) 15 liters of warm water at 35 ° C. were put into a color developing tank of an automatic developing machine, and 160 tablets for color developing replenishment for the color negative film were charged.
Dissolved. Next, 21 starters of the following formulation, which were separately tableted, were added as starter components, and after dissolution, warm water was added to the tank mark line to complete a tank liquid.

Color developing starter for color negative Sodium bromide 0.8 g Sodium iodide 2.0 mg Sodium bicarbonate 3.0 g Potassium carbonate 0.5 g Bleaching solution (5.0 l) Into a bleaching tank of an automatic developing machine, put 3.0 l of warm water at 35 ° C. 350 tablets for film replenishment were added and dissolved. Next, 10 starters of the following formulation, which were separately tableted, were added as starter components, and after dissolution, warm water was added up to the tank mark line to complete a tank liquid.

Bleaching starter for color negative Potassium bromide 10 g Sodium bicarbonate 1.5 g Potassium carbonate 3.5 g Fixing solution (4.5 L in the first tank, 4.5 L in the second tank) 35 ° C. in the first tank and the second tank of the automatic developing machine Warm water of 3.
0 l, and fixative replenishment tablet for color negative film
12 were charged and dissolved. Next, hot water was added up to the tank mark to complete the tank liquid.

Stabilizing solution (3.2 liters for each of first to third tanks) 3.0 liters of warm water at 35 ° C. were added to the first, second and third tanks of the fixing tank of the automatic developing machine, respectively. Were added and dissolved in 40 pieces at a time. Next, hot water was added up to the tank mark to complete the tank liquid.

Next, 20 pieces of each of the above-mentioned refill tablets were set in a refill tablet supply device provided to the automatic processing machine. The replenishing tablets are put into the color developing tank two by two when five 135-size 24-film films are processed, and one by one when two films are processed into the other tank, and simultaneously from the water supply device. Replenishing water was set so that 40 ml was supplied to the color developing tank, 10 ml to the bleaching tank, 40 ml to the fixing tank, and 80 ml to the stabilizing tank.

In the running test, 0.05 rounds per day were continuously processed until the total amount of water replenishment for color development became three times the volume of the color developing tank solution (3 rounds). The presence or absence of insoluble components in the processing tank of the automatic processing machine during running was observed. After running, the minimum and maximum reflection densities of the unexposed area of the color negative film sample were measured using a PDA-
It was measured using 65 (manufactured by Konica Corporation).

The results are shown in Table 12.

[0194]

[Table 12]

As is evident from Table 12, by containing the monosaccharide of the present invention as a preservative, it is possible to maintain good processability without increasing the permeation density in the Dmin part.

Example 9 A sample described in the example of Japanese Patent Application No. 3-47516 was exposed to light by a conventional method, and a running test was carried out using the following automatic developing machine and processing agent.

Automatic developing machine Konica Color Paper Type QA Processor CL-PP-71
The same tablet supply function, liquid level detection function, hot water supply function, etc. as in Example 8 were provided by modification in 8 and the following processing experiments were performed. The processing conditions are shown below.

Processing conditions 1 Processing step Processing temperature Processing time (seconds) Water replenishment amount Color development 35 ± 0.3 ° C 45 Table 13 Bleaching and fixing 35 ± 1.0 ° C 45 249 ml / m ² Stable 1 35 ± 3.0 ° C 30 Stable 2 35 ± 3.0 ℃ 30 Stable 3 35 ± 3.0 ℃ 30 249ml / m ² Drying 72 ± 5.0 ℃ 40 Processing condition 2 Processing step Processing temperature Processing time (second) Water replenishment Color development 38 ± 0.3 ℃ 27 Bleaching and fixing 38 ± 1.0 ℃ 27 249 mL / m ² a stable 1 38 ± 3.0 ℃ 30 stable 2 38 ± 3.0 ° C. 30 stable 3 38 ± 3.0 ℃ 30 249ml / m 2 drying 72 ± 5.0 ° C. 40 stabilizer supplemented to third reactor, successively 2 bath th A cascade system is used in which overflow liquid flows into the first tank.

Replenishing Tablet to be Used Replenishing Tablet for Color Development (I) The same operation as in Example 1 was repeated except that the weight ratio of CD-3 of the color developing agent was changed as shown in Table 13.
One thousand color developing and replenishing tablets for color paper were prepared.

Tablet for replenishing color development (II) Operation (A ') CD-3 [4-amino-3-methyl-N-ethyl-N- [β
-(Methanesulfonamido) ethyl] aniline sulfate]
Is ground in an air jet mill to an average particle size of 10 μm. This fine powder is granulated by spraying 4.0 ml of water for about 5 minutes at room temperature in a commercially available fluidized bed spray granulator, and the granulated product is dried at 60 ° C. for 10 minutes. Next, the granules are dried at 40 ° C. for 2 hours in a vacuum to remove the moisture of the granules almost completely. The amount of CD-3 is adjusted so that the weight ratio of CD-3 becomes the value shown in Table 13.

Operation (B ') 0.26 mol of the compound shown in Table 13 is ground and granulated in the same manner as in the operation (A'). The spray amount of water is 2.0 ml, and after granulation, 60 ° C
And dry for 10 minutes. Next, the granules are dried at 40 ° C. for 2 hours in a vacuum to remove the moisture of the granules almost completely.

Operation (C ') Tinopearl SFP (manufactured by Ciba Geigy) 19 g, sodium sulfite 1.3 g, potassium carbonate 256 g, potassium bromide 0.3 g,
After pulverizing 19 g of diethylenetriaminepentaacetic acid and 128 g of polyethylene glycol (average molecular weight: 6000) in the same manner as in (A '), they are uniformly mixed with a commercially available mixer. Then (A ')
In the same manner as described above, granulation is performed with the spray amount of water set to 150 ml.
After granulation, the granules are dried at 65 ° C. for 15 minutes, and then the granules are dried in vacuum at 40 ° C. for 2 hours to almost completely remove moisture from the granules.

Operation (D ') The granules prepared in the above operations (A') to (C ') were
Using a mixer in a room conditioned to a relative humidity of 40% or less
Mix for 1 minute, tough press collect made by Kikusui Seisakusho
Compression tableting was carried out using a modified tableting machine of 1527HU to produce 100 color development replenishing tablets for color paper.

This was repeated to prepare 1,000 tablets for color development replenishment.

Tablet for replenishing color development (III) Procedure (A ″) CD-3 [4-amino-3-methyl-N-ethyl-N- [β
-(Methanesulfonamido) ethyl] aniline sulfate]
Is ground in an air jet mill to an average particle size of 10 μm. This fine powder is granulated by spraying 4.0 ml of water for about 5 minutes at room temperature in a commercially available fluidized bed spray granulator, and the granulated product is dried at 60 ° C. for 10 minutes. Next, the granules are dried at 40 ° C. for 2 hours in a vacuum to remove the moisture of the granules almost completely. The amount of CD-3 is adjusted so that the weight ratio of CD-3 becomes the value shown in Table 13.

Operation (B ″) 0.13 mol of the compound shown in Table 13 is ground and granulated in the same manner as in the operation (A ″). Spray volume of water is 1.0ml, after granulation, 60 ℃
And dry for 10 minutes. Next, the granules are dried at 40 ° C. for 2 hours in a vacuum to remove the moisture of the granules almost completely.

Operation (C ″) 10 g of Tinopearl SFP (manufactured by Ciba Geigy), 0.6 g of sodium sulfite, 128 g of potassium carbonate, 0.17 of potassium bromide
g, 10 g of diethylenetriaminepentaacetic acid and 67 g of polyethylene glycol (average molecular weight: 6000) are ground in the same manner as in (A ″) and uniformly mixed with a commercially available mixer. Then, in the same manner as in (A ″), water is added. The granulation is performed with the spray amount of 100 ml. After granulation, the granules are dried at 65 ° C. for 15 minutes, and then the granules are dried in vacuum at 40 ° C. for 2 hours to almost completely remove moisture from the granules.

Operation (D ") The granules prepared in the above operations (A") to (C ") were treated at 25 ° C.
Using a mixer in a room conditioned to a relative humidity of 40% or less
Mix evenly for minutes. Next, this mixture was subjected to compression tableting using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho to produce 100 color developing and replenishing tablets for color paper.

This was repeated to prepare 1,000 tablets for replenishing color development.

Tablet for replenishing bleach-fixing Operation (E) 550 g of ferric potassium ethylenediaminetetraacetate monohydrate,
20 g of ethylenediaminetetraacetic acid is pulverized and granulated in the same manner as in the operation (A). Spray volume of water is 25.0ml, after granulation, 60 ℃
And dry for 15 minutes. Next, the granules are dried at 40 ° C. for 2 hours in a vacuum to remove the moisture of the granules almost completely.

Operation (F) 1770 g of potassium thiosulfate, 200 g of sodium sulfite, 60 g of potassium bromide and 20 g of p-toluenesulfinic acid are ground and granulated in the same manner as in the operation (A). Water spray amount is 15.0
After granulation, dry at 60 ° C for 10 minutes. Next, the granules are dried at 40 ° C. for 2 hours in a vacuum to remove the moisture of the granules almost completely.

Operation (G) The granules prepared in the above operations (E) and (F) are uniformly mixed for 10 minutes using a mixer in a room conditioned at 25 ° C. and a relative humidity of 40% or less. Next, the mixture was subjected to compression tableting repeatedly using a tableting machine modified from Kikusui Seisakusho's Tough Presto Collect 1527HU with a filling amount per tablet of 21.3 g, and 100 tablets.
A bleach-fix replenisher tablet for color paper was prepared.

By repeating this operation, 1200 tablets for replenishing bleach-fix were prepared.

Tablet for stable replenishment Procedure (H) 10 g of potassium carbonate and 200 g of sodium 1-hydroxyethane-1,1-diphosphonate were ground in the same manner as in the procedure (A).
Granulate. Spray volume of water is 1.0ml and after granulation,
Dry for minutes. Next, the granules are dried at 40 ° C. for 2 hours in a vacuum to remove the moisture of the granules almost completely.

Operation (I) 150 g of Tinopearl SFP, 300 g of sodium sulfite, 20 g of zinc sulfate heptahydrate and 150 g of ethylenediaminetetraacetic acid are pulverized and granulated in the same manner as in the operation (A). Water spray amount is 10.0
After granulation, the mixture is dried at 65 ° C. for 5 minutes. Next, the granules are dried at 40 ° C. for 8 hours in a vacuum to remove the moisture of the granules almost completely.

Operation (J) The granules prepared in the above operations (H) and (I) are uniformly mixed for 10 minutes using a mixer in a room conditioned at 25 ° C. and a relative humidity of 40% or less. Next, the mixture was subjected to compression tableting repeatedly using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho with the filling amount per tablet being 0.66 g to prepare 100 tablets for stable replenishment for color paper.

This operation was repeated to produce 800 tablets for stable replenishment.

Processing tank liquid to be used Color developing tank liquid (23.01) 18 l of warm water at 35 ° C. was placed in a color developing tank of an automatic developing machine, and 161 of the color developing and replenishing tablets for color paper were charged and dissolved. Next, 23 starters of the following formulation separately tableted as a starter component were added, and after dissolution, warm water was added up to the tank mark line to complete a tank liquid.

Color developing starter for color paper Potassium chloride 4.0 g Potassium hydrogen carbonate 4.8 g Potassium carbonate 2.1 g Bleaching / fixing solution (23.01) Add 15 liters of warm water at 35 ° C. to the bleach-fixing tank on an automatic developing machine, and replenish the bleaching for the color paper created 292 tablets were added and dissolved. After dissolution, warm water was added at the tank mark line to complete the tank liquid.

Stabilizing solution (1st to 3rd tanks, 15 l each) Into the first tank, the second tank, and the third tank of the automatic developing machine, 12 liters of warm water at 35 ° C. were added, and the prepared tablets for color paper stable replenishment were added. 60 pieces were added and dissolved. Next, hot water was added up to the tank mark to complete the tank liquid.

Each of the refilling tablets thus prepared was set in a refilling tablet supply device provided to the automatic processing machine in a quantity of 20 pieces. This refill tablet is 8000m in color paper for the color developing tank.
^{After the two} treatments, they were charged one by one, and the bleach-fixing tank and the stabilizing tank were set so that one was charged per 3200 cm ² . At the same time, the amount of water shown in Table 13 was set from the hot water supply device to the color developing tank, and 250 ml of water was supplied to the bleaching tank and the stabilizing tank when 1 m ² of color paper was processed.

In the running test, 0.05 rounds per day were continuously processed until the total amount of water replenishment for color development became three times the volume of the color developing tank solution (3 rounds). After the running, the minimum reflection density and the maximum reflection density of the unexposed area of the color paper sample were measured using PDA-65 (manufactured by Konica). Table 14 shows the results.

[0223]

[Table 13]

[0224]

[Table 14]

As is clear from Tables 13 and 14, the use of the monosaccharide preservative of the present invention provides good processing performance without increasing the reflection density of the Dmin part, and furthermore, the CD in the tablet. By increasing the weight ratio of -3, rapid processing and low waste liquidization can be realized.

[0226]

According to the present invention, the following effects can be obtained in a solid color developing solution for a silver halide color photographic light-sensitive material and a method for processing a silver halide color photographic light-sensitive material.

The storage stability and solubility of the solid processing agent are improved. The generation of stain during photographic processing is prevented. The stability of photographic performance during processing is improved. Reduction of packaging waste and reduction in replenishment Low waste liquefaction improves social environmental protection. In the case of tablets, excellent preservability and solubility can be maintained even in a one-part configuration.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing an example of an automatic developing machine used in a processing method of the present invention.

FIG. 2 is a schematic explanatory view showing an example of a replenishing agent replenishing device when a solidified tablet is used as the replenishing agent.

FIG. 3 is a schematic explanatory view showing an example of a replenishing water replenishing section of an automatic developing machine used in the processing method of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Color developing solution tank 2 Bleaching tank 3 Fixing tank 4 Washing tank 5 Stabilizing tank 6 Drying section 8 Replenishing agent replenishing device 10 Replenishing water replenishing device 16 Processing tank 20 Sub tank 21 Filtration device 22 Replenishing agent replenishing cam 23 Replenishing agent pushing Nail 24 Replenisher 25 Cartridge

Claims (11)

(57) [Claims] (1) at least one monosaccharide and paraphenylene;
Halide color containing amine diamine color developer
In solid color developing agents for photographic light-sensitive materials,
The content of phenylenediamine color developer is increased by weight
10% or more, and the solid color developing agent
Solid forms color developing agent characterized by containing no hydroxylamine salt. 2. The solid color developing agent according to claim 1, wherein the solid color developing agent is in the form of a tablet, a granule or a powder. 3. The solid color developing agent according to claim 1, wherein the solid color developing agent is in the form of a tablet. 4. The solid color developing agent according to claim 1, wherein said solid color developing agent comprises one agent. 5. The para-phenylenediamine-based color development
The agent is 4-amino-N-ethyl-N- (β-methanesulfonamide
Ethyl) -m-toluidine (sesquisulfate hydrate)
5. The method according to claim 1, wherein
Item 6. The solid color developing agent according to item 1 . 6. A paraphenylene comprising at least one monosaccharide.
Halide color containing amine diamine color developer
In a solid color developing agent for a photographic material, the solid
Low concentration when the color developing agent is dissolved as a working solution
At least 1.5 × 10 ^-2 mol / l and the solid color appearance
Solid forms color developing agent you characterized in that the image processing agent does not contain a hydroxylamine salt. 7. The solid color developing agent is in the form of tablets or granules.
7. The solid color developing agent according to claim 6, which is in the form of a solid or a powder. 8. The solid color developing agent is in the form of a tablet.
The solid color developing agent according to claim 6 or 7, wherein: 9. The solid color developing agent comprises one agent.
9. The method according to claim 6, 7 or 8, wherein
Solid color developing agent . 10. The paraphenylenediamine-based color former
When the imaging agent is 4-amino-N-ethyl-N- (β-methanesulfonami
Doechiru) -m- toluidine (Sesukisarufe Tohidore
10), characterized in that:
Item 2. The solid color developing agent according to Item 1. 11. An image forming method using a silver halide color photographic light-sensitive material.
After continuous exposure using an automatic processor
Wherein when replenishing in the color developing tank,
Color developing the solid color developing agent according to any one of the above.
It is characterized by being added and dissolved at the site that comes in contact with the processing solution
For processing silver halide color photographic light-sensitive materials.